EP1310271B1 - Elektrodenanordnung für Verwendungen einer implantierbaren Vorrichtung, die den electiven Ersetzungsindikator (ERI) benötigen - Google Patents

Elektrodenanordnung für Verwendungen einer implantierbaren Vorrichtung, die den electiven Ersetzungsindikator (ERI) benötigen Download PDF

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EP1310271B1
EP1310271B1 EP02257777A EP02257777A EP1310271B1 EP 1310271 B1 EP1310271 B1 EP 1310271B1 EP 02257777 A EP02257777 A EP 02257777A EP 02257777 A EP02257777 A EP 02257777A EP 1310271 B1 EP1310271 B1 EP 1310271B1
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svo
active material
medical device
cathode active
cathode
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EP1310271A3 (de
EP1310271A2 (de
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Hong Gan
Esther S. Takeuchi
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Greatbatch Inc
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Greatbatch Inc
Wilson Greatbatch Technologies Inc
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61N—ELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY
    • A61N1/00—Electrotherapy; Circuits therefor
    • A61N1/18—Applying electric currents by contact electrodes
    • A61N1/32—Applying electric currents by contact electrodes alternating or intermittent currents
    • A61N1/36—Applying electric currents by contact electrodes alternating or intermittent currents for stimulation
    • A61N1/362—Heart stimulators
    • A61N1/37—Monitoring; Protecting
    • A61N1/3706—Pacemaker parameters
    • A61N1/3708—Pacemaker parameters for power depletion
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/48—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/40—Alloys based on alkali metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/54—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of silver
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/669—Steels
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/40—Alloys based on alkali metals
    • H01M4/405—Alloys based on lithium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
    • H01M6/164—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solvent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
    • H01M6/166—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solute
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • This invention relates to the conversion of chemical energy to electrical energy.
  • the present invention relates to an implantable medical device powered by an alkali metal electrochemical cell, such as of lithium coupled with a sandwich cathode.
  • the sandwich cathode design comprises a second cathode active material of a relatively high energy density but of a relatively low rate capability sandwiched between two current collectors with a first cathode active material having a relatively low energy density but of a relatively high rate capability in contact with the opposite sides of the current collectors.
  • the present invention then provides an indicator as to when the cell's discharge capacity is nearing end-of-life (EOL) based on the theoretical capacity and the discharge efficiency of the first and second cathode active materials. This early warning is defined as the elective replacement indicator (ERI) and signals a physician when it is time to replace the medical device.
  • Suitable medical devices include cardiac defibrillators, neurostimulators, pacemakers, and the like.
  • the Li/SVO cell system has been used as the power source for implantable cardiac defibrillator applications requiring high rate pulse capability, i.e., about 1 to 4 about 4 amps.
  • a pre-determined background voltage is generally used as the ERI. This pre-determined voltage value varies depending on the cell size, theoretical capacity and the associated device design. Additionally, due to the characteristic voltage delay and Rdc growth that occurs at about the 2.6-volt plateau, a pre-determined Rdc or voltage value under high current pulsing is sometimes used as an ERI indicator. Consequently, the ERI indicator selection is very complicated and dependent on the individual device design of each manufacturer.
  • the Li/CF x system provides medium rate discharge capability (mA range). This cell is a good power source for devices like implantable neurostimulators and implantable devices that treat cardiac heart failure (CHF). Although the Li/CF x system has very high energy density, its discharge voltage profile is mostly flat ( ⁇ 2.8V). Near the end of discharge, however, a sharp voltage drop occurs. This unfavorable characteristic voltage profile makes it very difficult to set the ERI accurately for Li/CF x cells. In order to resolve this problem, mixtures of CF x and other cathode materials, for example SVO, are proposed.
  • the capacity contribution from each voltage plateau region during cell discharge is dependent on the initial capacity ratio between the SVO and CF x materials in the cathode construction.
  • the ratio of SVO to CF x in the cathode it is possible to control the capacity contribution of the cell at various voltage plateau regions.
  • ERI voltage is defined as about 2.6 volts (or any voltage between about 2.65 volts to about 2.5 volts) and EOL is defined as about 2.4 volts (or any voltage between about 2.5 volts to about 2.0 volts, or even lower for low rate cells)
  • ERI voltage is defined as about 2.6 volts (or any voltage between about 2.65 volts to about 2.5 volts)
  • EOL is defined as about 2.4 volts (or any voltage between about 2.5 volts to about 2.0 volts, or even lower for low rate cells)
  • varying the SVO to CF x capacity ratio provides a means for calculating both ERI and EOL.
  • a mechanism for determining both EOL and ERI is provided by varying the relative weight of SVO to CF x in a cathode having one of the following configurations: SVO/current collector/CF x /current collector/SVO, SVO/current collector/SVO/CF x /SVO/current collector/SVO, SVO/current collector/CF x with the SVO facing the anode, and SVO/current collector/SVO/CF x with the SVO facing the anode.
  • the capacity ratio of SVO:CF x is achieved ranging from 1:50 to 10:1.
  • the cathode is not a mixture, but discrete layers of the active materials, the rate capability is not compromised by changes in the SVO/CF x ratio.
  • pulse means a short burst of electrical current of significantly greater amplitude than that of a pre-pulse current immediately prior to the pulse.
  • a pulse train consists of at least two pulses of electrical current delivered in relatively short succession with or without open circuit rest between the pulses.
  • An exemplary pulse train may consist of four 10-second pulses of about 0.5 mA/cm 2 to about 50 mA/cm 2 with a 15 second rest between each pulse.
  • An electrochemical cell that possesses sufficient energy density and discharge capacity required to meet the vigorous requirements of implantable medical devices comprises an anode of a metal selected from Groups IA, IIA and IIIB of the Periodic Table of the Elements.
  • Such anode active materials include lithium, sodium, potassium, etc., and their alloys and intermetallic compounds including, for example, Li-Si, Li-Al, Li-B and Li-Si-B alloys and intermetallic compounds.
  • the preferred anode comprises lithium.
  • An alternate anode comprises a lithium alloy such as a lithium-aluminum alloy. The greater the amounts of aluminum present by weight in the alloy, however, the lower the energy density of the cell.
  • the form of the anode may vary.
  • the anode is a thin metal sheet or foil of the anode metal pressed or rolled on a metallic anode current collector, preferably comprising titanium, titanium alloy or nickel. Copper, tungsten and tantalum are also suitable materials for the anode current collector.
  • the anode current collector has an integral tab or lead contacted by a weld to a cell case of conductive metal in a case-negative electrical configuration.
  • the anode may be formed in some other geometry, such as a bobbin shape, cylinder or pellet to allow an alternate low surface cell design.
  • the electrochemical cell further comprises a cathode of electrically conductive cathode active materials.
  • the cathode is preferably of solid active materials and the electrochemical reaction at the cathode involves conversion of ions that migrate from the anode to the cathode into atomic or molecular forms.
  • the cathode may comprise a first active material of a metal element, a metal oxide, a mixed metal oxide and a metal sulfide, and combinations thereof and a second active material of a carbonaceous chemistry.
  • the first cathode active material has a relatively lower energy density but a relatively higher rate capability than the second cathode active material.
  • the first cathode active material is formed by the chemical addition, reaction, or otherwise intimate contact of various metal oxides, metal sulfides and/or metal elements, preferably during thermal treatment, sol-gel formation, physical vapor deposition, chemical vapor deposition or hydrothermal synthesis in mixed states.
  • the active materials thereby produced contain metals, oxides and sulfides of Groups IB, IIB, IIIB, IVB, VB, VIB, VIIB and VIII, which includes the noble metals and/or other oxide and sulfide compounds.
  • One preferred metal oxide of a relatively high rate capability but a relatively low energy density has the general formula SM x V 2 O y where SM is a metal selected from Groups IB to VIIB and VIII of the Periodic Table of Elements, wherein x is about 0.30 to 2.0 and y is about 4.5 to 6.0 in the general formula.
  • Another preferred metal oxide cathode material of a relatively high rate capability but a relatively low energy density includes V 2 O z wherein z ⁇ 5 combined with Ag 2 O with silver in either the silver(II), silver(I) or silver(0) oxidation state and CuO with copper in either the copper(II), copper(I) or copper(0) oxidation state.
  • This mixed metal oxide has the general formula CU x Ag y V 2 O z . (CSVO) and the range of material compositions is preferably about 0.01 ⁇ z ⁇ 6.5.
  • Typical forms of CSVO are Cu 0.16 Ag 0.67 V 2 O z with z being about 5.5 and Cu 0.5 Ag 0.5 V 2 O z with z being about 5.75.
  • the oxygen content is designated by z since the exact stoichiometric proportion of oxygen in CSVO can vary depending on whether the cathode material is prepared in an oxidizing atmosphere such as air or oxygen, or in an inert atmosphere such as argon, nitrogen and helium.
  • an oxidizing atmosphere such as air or oxygen
  • an inert atmosphere such as argon, nitrogen and helium.
  • the sandwich cathode design of the present invention further includes a second active material of a relatively high energy density and a relatively low rate capability in comparison to the first cathode active material.
  • the second active material is preferably a carbonaceous compound prepared from carbon and fluorine, which includes graphitic and nongraphitic forms of carbon, such as coke, charcoal or activated carbon.
  • Fluorinated carbon is represented by the formula (CF x ) n wherein x varies between about 0.1 to 1.9 and preferably between about 0.5 and 1.2, and (C 2 F) n wherein the n refers to the number of monomer units which can vary widely.
  • the first active material of the sandwich cathode design is any material which has a relatively lower energy density but a relatively higher rate capability than the second active material.
  • V 2 O 5 , MnO 2 , LiCoO 2 , LiNiO 2 , LiMnO 2 , LiMn 2 O 4 , TiS 2 , Cu 2 S, FeS, FeS 2 , copper oxide, copper vanadium oxide, and mixtures thereof are useful as the first active material.
  • the first and second active materials are preferably mixed with a binder material such as a powdered fluoro-polymer. More preferably, powdered polytetrafluoroethylene or powdered polyvinylidene fluoride are present in the cathode mixture at, by weight, about 1% to about 5%.
  • a conductive diluent is preferably added to the cathode mixture to improve conductivity.
  • Suitable materials for this purpose include acetylene black, carbon black and/or graphite or a metallic powder such as-powdered nickel, aluminum, titanium and stainless steel.
  • the preferred-cathode active mixture thus includes, by weight, a powdered fluoro-polymer binder present at about 3%, a conductive diluent present at about 3% and about 94% of the cathode active material.
  • Cathode components for incorporation into an electrochemical cell according to the present invention may be prepared by rolling, spreading or pressing the first and second cathode active materials onto a suitable current collector selected from the group consisting of stainless steel, titanium, tantalum, platinum and gold.
  • the preferred current collector material is titanium, and most preferably the titanium cathode current collector has a thin layer of graphite/carbon paint, gold, iridium, palladium, platinum, rhodium, ruthenium, and mixtures-thereof provided thereon.
  • Cathodes prepared as described above may be in the form of one or more plates operatively associated with at least one or more plates of anode material, or in the form of a strip wound with a corresponding strip of anode material in a structure similar to a "jellyroll".
  • SVO cathode material which provides a relatively high power or rate capability but a relatively low energy density or volumetric capability and CF x cathode material, which has a relatively high energy density but a relatively low rate capability, are individually pressed on opposite sides of a current collector, so that both materials are in direct contact therewith. Therefore, one exemplary cathode electrode has the following configuration: SVO / current collector / C ⁇ F x / current collector / SVO An important aspect of the present invention is that the high rate cathode material (in-this case the SVO material) maintains direct contact with the current collector.
  • Another embodiment has the high capacity/low rate material sandwiched between the high rate-cathode materials, in which the low rate/high capacity material is in direct contact with the high rate material.
  • This cathode design has the following configuration: SVO / current collector / SVO / C ⁇ F x / SVO / current collector / SVO
  • the high capacity material having the low rate capability is preferably positioned between two layers of high rate cathode material (either high or low capacities) This is shown in configurations 1 and 2 above.
  • the exemplary CF x material never directly faces the lithium anode.
  • the low rate cathode material must be short circuited with the high rate material, either by direct contact as demonstrated above in configuration 2, or by parallel connection through the current collectors as in configuration 1.
  • Additional embodiments have the configurations: SVO / current collector / C ⁇ F x SVO / current collector / SVO / C ⁇ F x
  • the sandwich cathode is separated from the Group IA. IIA or IIIB anode by a suitable separator material.
  • the separator is of an electrically insulative material, is chemically unreactive with the anode and cathode active materials and is both chemically unreactive with and insoluble in the electrolyte.
  • the separator material has sufficient porosity to allow flow there through of the electrolyte during the electrochemical reaction of the cell.
  • Illustrative separator materials include fabrics woven from fluoropolymeric fibers including polyvinylidine fluoride, polyethylenetetrafluoroethylene; and polyethylenechlorotrifluoroethylene used either alone or laminated with a fluoropolymeric microporous film, non-woven glass, polypropylene, polyethylene, glass fiber materials, ceramics, a polytetrafluoroethylene membrane commercially available under the designation ZITEX (Chemplast Inc.), a polypropylene membrane commercially available under the designation CELGARD (Celanese Plastic Company, Inc.) and a membrane commercially available under the designation DEXIGLAS (C.H. Dexter, Div., Dexter Corp.).
  • fluoropolymeric fibers including polyvinylidine fluoride, polyethylenetetrafluoroethylene; and polyethylenechlorotrifluoroethylene used either alone or laminated with a fluoropolymeric microporous film, non-woven glass, polypropylene, polyethylene
  • the electrochemical cell of the present invention further includes a nonaqueous, ionically conductive electrolyte that serves as a medium for migration of ions between the anode and the cathode electrodes during the cell's electrochemical reactions.
  • Nonaqueous electrolytes suitable for the present invention are substantially inert to the anode and cathode materials, and they exhibit those physical properties necessary for ionic transport, namely, low viscosity, low surface tension and wettability.
  • a suitable electrolyte has an inorganic, ionically conductive alkali metal salt dissolved in a mixture of aprotic organic solvents comprising a low viscosity solvent and a high permittivity solvent.
  • the salt is selected from LiPF 6 , LiBF 4 , LiAsF 6 , LiSbF 6 , LiClO 4 , LiO 2 , LiAlCl 4 , LiGaCl 4 , LiC(SO 2 CF 3 ) 3 , LiN(SO 2 CF 3 ) 2 , LiSCN, LiO 3 SCF 3 , LiC 6 F 5 SO 3 , LiO 2 CCF 3 , LiSO 6 F, LiB(C 6 H 5 ) 4 and LiCF 3 SO 3 , and mixtures thereof.
  • Low viscosity solvents useful with the present invention include esters, linear and cyclic ethers and dialkyl carbonates such as tetrahydrofuran (THF), methyl acetate (MA), diglyme, trigylme, tetragylme, dimethyl carbonate (DMC), 1,2-dimethoxyethane (DME), 1,2-diethoxyethane (DEE), 1-ethoxy,2-methoxyethane (EME), ethyl methyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, diethyl carbonate, dipropyl carbonate, and mixtures thereof.
  • THF tetrahydrofuran
  • MA methyl acetate
  • DMC 1,2-dimethoxyethane
  • DEE 1,2-diethoxyethane
  • EME 1-ethoxy,2-methoxyethane
  • ethyl methyl carbonate methyl propyl carbonate
  • High permittivity solvents include cyclic carbonates, cyclic esters and cyclic amides such as propylene carbonate (PC), ethylene carbonate (EC), butylene carbonate, acetonitrile, dimethyl sulfoxide, dimethyl formamide, dimethyl acetamide, ⁇ -valerolactone, Y-butyrolactone (GBL), N-methylpyrrolidinone (NMP), and mixtures thereof.
  • the preferred anode is lithium metal and the preferred electrolyte is 0.8M to 1.5M LiAsF 6 or LiPF 6 dissolved in a 50:50 mixture, by volume, of propylene carbonate and 1,2-dimethoxyethane.
  • Cells of the present invention having the first cathode material of a relatively lower energy density but a relatively higher power capability than that of the second cathode material are characterized by several voltage plateaus in their discharge profile.
  • the voltage profile initially follows the characteristic first voltage plateau of the SVO material at about 3.2 volts. The cell voltage then drops to another plateau at about 2.8 volts, which is primarily contributed by discharge of the CF x material. Then, the voltage profile follows the characteristic second plateau of the SVO material at about 2.6 volts. From about 2.5 volts to EOL ( ⁇ 2.0 volts) both the SVO and CF x materials contribute to cell discharge. Based on this, the capacity contribution from each voltage plateau region during cell discharge is highly dependent on the initial capacity ratio between the SVO and CF x materials (SVO:CF x ratio) in the cathode construction.
  • the ratio of SVO to CF x in the cathode it is possible to control the capacity contribution of the cell at various voltage plateau regions.
  • the ERI voltage any voltage between about 2.65 volts to about 2.4 volts
  • the EOL voltage any voltage between about 2.5 volts to about 2.0 volts, or even lower for low rate cells
  • A is the defined capacity from ERI to EOL
  • B is the theoretical capacity of the cell
  • C is the efficiency of the SVO material in delivered capacity from ERI to EOL based on percent of the material's theoretical capacity
  • D is the efficiency of CF x material in delivered capacity from ERI to EOL based on percent of the material's theoretical capacity.
  • a typical Li/SVO/CF x cell may be built having its ERI defined as a background discharge voltage of 2.6 volts and EOL defined as a background discharge voltage of 2.4V.
  • ERI defined as a background discharge voltage of 2.6 volts
  • EOL defined as a background discharge voltage of 2.4V.
  • the estimated value for constants C and D are 32.1% and 13.8%, respectively.
  • the C constant for SVO is estimated based on the 18 month accelerated discharge data (ADD) regime at 37°C of a Li/SVO cell.
  • An 18-month ADD regime consists of a pulse train comprising four 22 mA/cm 2 to 50 mA/cm 2 , 10 second pulses with 15 seconds rest between each pulse. The pulse density is predicated on the cell capacity. One such pulse train is superimposed on the background load about every 45 days.
  • the 18-month ADD is designed to deplete the cells of 100% of their theoretical capacity in 18 months.
  • Fig. 1 demonstrates application of equation 5 in determining deliverable capacity between any two-background voltage points.
  • a Li/SVO/CF x cell having a theoretical capacity (B) of 2.5 Ah, as indicated by arrow 10 on the graph, and a SVO:CF x ratio of 1.1 (arrow 12).
  • the C and D constants are 0.321 and 0.138, respectively. Curves 10 and 12 intersect at point 14 on the graph.
  • the cell's discharge capacity (A) from ERI to EOL is determined to be about .58 Ah. This corresponds with the graph by reading over to the ordinate from point 14 to find that the deliverable capacity from ERI to EOL is about .58 Ah, as indioated by arrow 16.
  • Figs. 2 and 3 show a patient P having a medical device 20, such as an implantable cardiac defibrillator, implanted inside the body.
  • a medical device 20 such as an implantable cardiac defibrillator, implanted inside the body.
  • An enlarged schematic of the medical device 20 is shown in Fig. 3 comprising a housing 22 containing control circuitry 24 powered by an electrochemical cell 26 of the present invention.
  • the control circuitry 24 is connected to at least one conductor 28 by a hermetic feedthrough 30, as is well known by those skilled in the art.
  • the distal end of the conductor connects to the heart H for delivering a therapy thereto.
  • the patient will go to a medical facility, and the like, where the deliverable capacity determined by the control circuitry 24 is read to determine if the cell has discharged to the point that it is between the ERI and EOL voltages. If so, this indicates that it is time for the physician to schedule the patient for surgery to replace the medical device with a new one.
  • SVO and CF x active materials reach end of life at the same time. This is the case in spite of the varied usage in actual implantable medical device application. Since both electrode materials reach end of service life at the same time, no energy capacity is wasted.

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Claims (13)

  1. Implantierbare medizinische Vorrichtung, die folgendes aufweist:
    a) ein Gehäuse
    b) eine Steuerschaltung, die in dem Gehäuse untergebracht ist, um die Funktion der medizinischen Vorrichtung zu steuern;
    c) eine elektrochemische Zelle, die in dem Gehäuse untergebracht ist, um die Steuerschaltung mit Leistung zu versorgen, wobei die Zelle folgendes aufweist:
    i) eine Anode;
    ii) eine Kathode aus einem ersten kathodenaktiven Material, das sich von einem zweiten kathodenaktiven Material unterscheidet, wobei das erste kathodenaktive Material eine erste Energiedichte und einen ersten Nennstrom aufweist und das zweite kathodenaktive Material eine zweite Energiedichte und einen zweiten Nennstrom aufweist, wobei das erste kathodenaktive Material mit einer Seite eines Stromabnehmers kontaktiert ist und auf die Anode gerichtet ist, wobei das zweite kathodenaktive Material sich auf der gegenüber liegenden Seite des Stromabnehmers befindet, und wobei die erste Energiedichte des ersten kathodenaktiven Materials unter der Energiedichte des zweiten kathodenaktiven Materials liegt, während der erste Nennstrom des ersten kathodenaktiven Materials über dem zweiten Nennstrom des zweiten kathodenaktiven Materials liegt; und
    iii) einen Elektrolyten, der die Anode und die Kathode aktiviert; und
    d) einen Leiter zum Verbinden der medizinischen Vorrichtung mit einem Körper, der von der medizinischen Vorrichtung unterstützt werden soll;
    dadurch gekennzeichnet, dass
    e) die verfügbare Kapazität der Zelle von der ERI-Spannung zur EOL-Spannung (A) von der Steuerschaltung mittels der Gleichung: A/B = [C x ein Verhältnis einer ersten theoretischen Kapazität des ersten kathodenaktiven Materials : einer zweiten theoretischen Kapazität des zweiten kathodenaktiven Materials + D] / (das Verhältnis der ersten theoretischen Kapazität : der zweiten theoretischen Kapazität + 1) bestimmt werden kann, wobei A die Entladungskapazität der Zelle von einer ERI (Elective Replacement Indicator)-Spannung zu einer EOL (End of Life)-Spannung ist und B die theoretische Kapazität der Zelle ist,
    wobei C und D die Wirkungsgrade des ersten bzw. des zweiten kathodenaktiven Materials in Bezug auf die verfügbare Kapazität von der ERI-Spannung zur EOL-Spannung auf Prozentbasis der theoretischen Kapazität des Materials ist; und
    f) wobei die Steuerschaltung die verfügbare Kapazität der Zelle bestimmt, so dass die verfügbare Kapazität der Zelle ausgelesen werden kann, um zu bestimmen, ob die Zelle bis zu dem Punkt entladen wurde, dass sie zwischen ERI- und EOL-Spannung liegt.
  2. Medizinische Vorrichtung nach Anspruch 1, wobei das zweite kathodenaktive Material ausgewählt ist aus der Gruppe, bestehend aus CFx, Ag2O, Ag2O2, CuF, Ag2CrO4, MnO2, SVO und deren Mischungen.
  3. Medizinische Vorrichtung nach Anspruch 1 oder Anspruch 2, wobei das erste kathodenaktive Material ausgewählt ist aus der Gruppe, bestehend aus SVO, CSVO, V2O5, MnO2, LiCoO2, LiNiO2, LiMnO2, LiMn2O4, CuO2, TiS2, Cu2S, FeS, FeS2, Kupferoxid, Kupfervanadiumoxid und deren Mischungen.
  4. Medizinische Vorrichtung nach Anspruch 1, wobei das erste kathodenaktive Material SVO ist und das zweite kathodenaktive Material CFx ist.
  5. Medizinische Vorrichtung nach Anspruch 4, wobei die ERI-Spannung etwa 2,65 Volt bis etwa 2,4 Volt ist.
  6. Medizinische Vorrichtung nach Anspruch 4 oder Anspruch 5, wobei die EOL-Spannung etwa 2,5 Volt bis etwa 2,0 Volt beträgt.
  7. Medizinische Vorrichtung nach einem der Ansprüche 4 bis 6, wobei das Kapazitätsverhältnis von SVO : CFx bei etwa 1 : 50 bis etwa 10 : 1 liegt.
  8. Medizinische Vorrichtung nach einem der Ansprüche 4 bis 7, wobei der Stromabnehmer ausgewählt ist aus der Gruppe bestehend aus Edelstahl, Titan, Tantal, Platin, Gold, Aluminium, Cobalt-Nickel-Legierungen, hochlegiertem ferritischem Edelstahl, der Molybdän und Chrom enthält, und nickel-, chrom- und molybdänhaltigen Legierungen.
  9. Medizinische Vorrichtung nach einem der Ansprüche 4 bis 8, einschließlich der Ausstattung mit einem Stromabnehmer aus Titan, der mit einer Beschichtung versehen ist, die ausgewählt ist aus der Gruppe bestehend aus Graphit/Kohlenstoff-Material, Gold, Iridium, Palladium, Platin, Rhodium, Ruthenium und deren Mischungen.
  10. Medizinische Vorrichtung nach einem der Ansprüche 4 bis 9, wobei die Kathode folgendermaßen aufgebaut ist: SVO / erster Stromabnehmer / CFx / zweiter Stromabnehmer / SVO.
  11. Medizinische Vorrichtung nach einem der Ansprüche 4 bis 9, wobei die Kathode folgendermaßen aufgebaut ist: SVO / erster Stromabnehmer / SVO / CFx / SVO/zweiter Stromabnehmer / SVO.
  12. Medizinische Vorrichtung nach einem der Ansprüche 4 bis 9, wobei Anode aus Lithium besteht und die Kathode folgendermaßen aufgebaut ist: SVO / Stromabnehmer / CFx, wobei das SVO auf die Lithiumanode gerichtet ist.
  13. Medizinische Vorrichtung nach einem der Ansprüche 4 bis 9, wobei die Anode aus Lithium besteht und die Kathode folgendermaßen aufgebaut ist: SVO / Stromabnehmer / SVO / CFx, wobei das SVO auf die Lithiumanode gerichtet ist.
EP02257777A 2001-11-09 2002-11-11 Elektrodenanordnung für Verwendungen einer implantierbaren Vorrichtung, die den electiven Ersetzungsindikator (ERI) benötigen Expired - Lifetime EP1310271B1 (de)

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Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6849360B2 (en) 2002-06-05 2005-02-01 Eveready Battery Company, Inc. Nonaqueous electrochemical cell with improved energy density
US10252062B2 (en) * 2003-02-15 2019-04-09 Medtronic, Inc. Replacement indicator timer for implantable medical devices
US7776470B2 (en) 2005-09-28 2010-08-17 Greatbatch Ltd. Anode-to-cathode capacity ratios for SVO/CF x hybrid cathode electrochemical cells
WO2007040547A1 (en) * 2005-10-05 2007-04-12 California Institute Of Technology Subfluorinated graphite fluorides as electrode materials
US7646170B2 (en) * 2006-05-11 2010-01-12 Greatbatch Ltd. Method of selecting replacement indicating voltage for an implantable electrochemical cell
US20070281213A1 (en) * 2006-06-02 2007-12-06 Gentcorp Ltd. Carbon Monofluoride Cathode Materials Providing Simplified Elective Replacement Indication
US8192867B2 (en) 2006-10-03 2012-06-05 Greatbatch Ltd. Hybrid cathode design for an electrochemical cell
US8364276B2 (en) 2008-03-25 2013-01-29 Ebr Systems, Inc. Operation and estimation of output voltage of wireless stimulators
US8588926B2 (en) 2008-03-25 2013-11-19 Ebr Systems, Inc. Implantable wireless accoustic stimulators with high energy conversion efficiencies
JP5599810B2 (ja) * 2008-11-07 2014-10-01 イーグルピッチャー テクノロジーズ，エルエルシー 非結晶性または半結晶性の銅−マンガンの酸化物カソード材料である非水性セル
US8663825B2 (en) * 2009-03-05 2014-03-04 Eaglepicher Technologies, Llc End of life indication system and method for non-aqueous cell having amorphous or semi-crystalline copper manganese oxide cathode material
JP5528534B2 (ja) * 2009-03-18 2014-06-25 イーグルピッチャー テクノロジーズ，エルエルシー 少なくとも３種のカソード材料の混合物を有する非水電気化学セル
JP5599866B2 (ja) * 2009-04-06 2014-10-01 イーグルピッチャー テクノロジーズ，エルエルシー 熱電池のカソード材料およびそれを含有する電池
WO2010117954A1 (en) * 2009-04-06 2010-10-14 Eaglepicher Technologies, Llc Thermal battery electrolyte compositions, electrode-electrolyte composites, and batteries including the same
US8652674B2 (en) 2010-06-24 2014-02-18 Eaglepicher Technologies, Llc Thermal battery cathode materials containing nickel disulfide and batteries including same
US11654287B2 (en) 2019-08-30 2023-05-23 Ebr Systems, Inc. Pulse delivery device including slew rate detector, and associated systems and methods

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Publication number Priority date Publication date Assignee Title
US5370668A (en) 1993-06-22 1994-12-06 Medtronic, Inc. Fault-tolerant elective replacement indication for implantable medical device
US5569553A (en) * 1995-03-08 1996-10-29 Wilson Greatbatch Ltd. Battery design for achieving end-of-life indication during electrical discharge
US6551747B1 (en) 2000-04-27 2003-04-22 Wilson Greatbatch Ltd. Sandwich cathode design for alkali metal electrochemical cell with high discharge rate capability

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EP1310271A2 (de) 2003-05-14
DE60221771D1 (de) 2007-09-27
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US20030104269A1 (en) 2003-06-05

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